Water → 2-(((3-methyl-4-(1,5,9-trioxaspiro[5.5]undec-3-ylmethoxy)pyridin-2-yl)methyl)sulfinyl)-1H-benzimidazole

HRID 31622

反応式

HRID 31622 の反応式
O.[CH3:2][C:3]1[C:4]([CH2:22][S:23][C:24]2[NH:28][C:27]3[CH:29]=[CH:30][CH:31]=[CH:32][C:26]=3[N:25]=2)=[N:5][CH:6]=[CH:7][C:8]=1[O:9][CH2:10][CH:11]1[CH2:16][O:15][C:14]2([CH2:21][CH2:20][O:19][CH2:18][CH2:17]2)[O:13][CH2:12]1.C(N(CC)C(C)C)(C)C.[O-]O.C1(C(C)C)C=CC=CC=1.C(=O)([O-])[OH:54].[Na+]>CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].C1(C)C=CC=CC=1>[CH3:2][C:3]1[C:4]([CH2:22][S:23]([C:24]2[NH:25][C:26]3[CH:32]=[CH:31][CH:30]=[CH:29][C:27]=3[N:28]=2)=[O:54])=[N:5][CH:6]=[CH:7][C:8]=1[O:9][CH2:10][CH:11]1[CH2:16][O:15][C:14]2([CH2:17][CH2:18][O:19][CH2:20][CH2:21]2)[O:13][CH2:12]1

参加物

8

反応物 5

HCID 962WaterHCID 81531DiisopropylethylamineHCID 516892Sodium BicarbonateHCID 53627471Cumen hydroperoxideHCID 597925582-(((3-methyl-4-(1,5,9-trioxaspiro[5.5]undec-3-ylmethoxy)pyridin-2-yl)methyl)thio)-1H-benzimidazole2 回

生成物 1

HCID 120032132-(((3-methyl-4-(1,5,9-trioxaspiro[5.5]undec-3-ylmethoxy)pyridin-2-yl)methyl)sulfinyl)-1H-benzimidazole収率 82.4%

試薬・触媒・溶媒 2

HCID 11026Titanium isopropoxide触媒HCID 1140Toluene溶媒

反応条件

温度
50 °C

実験手順

To a toluene (dehydrated)(1.5 ml)-water (1.47 μl, 81.5 μmol) solution of the 2-(((3-methyl-4-(1,5,9-trioxaspiro[5.5]undec-3-ylmethoxy)pyridin-2-yl)methyl)thio)-1H-benzimidazole (300 mg, 679 mmol) separately obtained in the same manner as described in the steps (10a) to (10d) of Example 10, L-(+)-diethyl tartrate (51.2 μl, 299 μmol) was added and the mixture was stirred at 50° C. for 5 minutes in a nitrogen atmosphere. Titanium (IV) isopropoxide (40.1 μl, 136 μmol) was added and the resultant mixture was stirred for further one hour. After cooled on ice and N,N-diisopropylethylamine (37.8 μl, 217 μmol) was added, and cumene hydroperoxide (376 μl, 2.04 mmol as the content was regarded as 80%) was added dropwise in a nitrogen atmosphere, the mixture was stirred at 0° C. to room temperature for 5.5 hours. After a saturated aqueous solution of sodium hydrogen carbonate was added, the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (NH silica gel, elution solvent: ethyl acetate/methanol) to obtain the title compound (256 mg, yield: 82.4%) as a light yellow foam.

後処理

  1. additionwas added
  2. additionwas added
  3. additionwas added dropwise in a nitrogen atmosphere
  4. stirringthe mixture was stirred at 0° C. to room temperature for 5.5 hours
  5. extractionthe reaction mixture was extracted with ethyl acetate
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. distillationthe solvent was distilled off under reduced pressure
  8. customThe obtained residue was purified by silica gel column chromatography (NH silica gel, elution solvent: ethyl acetate/methanol)

出典と根拠

ORDレコード
ord-d46419c99e174cbf8f61c741ee942438
出典データセット
uspto-grants-2008_09
特許番号
US07425634B2

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